Stereochemistry defined

Hamilton, J. G. C Hooper, A. M., Ibbotson, H. C. el al. (1999b). 9-Methylgermacrene-B is confirmed as the sex pheromone of the sandfly Lutzomyia longipalpis from Lapinha, Brazil, and the absolute stereochemistry defined as S. Chemical Communications 2335-2336. 

It was one of the first phosphorinanes to have its stereochemistry defined in solution by... 

Pharmaceutical compounds—drugs—are generally small to medium-sized organic molecules. Many are chiral. When this is the case, either a pure enantiomer or a racemic mixture may be used in therapy. Generally, the physiological effects of enantiomeric and racemic forms of a pharmaceutical compound are different. Drug development therefore involves the testing of both enantiomeric and racemic forms of candidate compounds. Before this can be carried out, the enantiomers of the compound of interest must be obtained and their stereochemistry defined. 

Additional insight into the competition between the various cyclic transition states is provided by a recent study of the reactions of crotylboronates (22) and (23) with the two isomers of oxime silyl ether (24 Scheme 8). The stereoselectivities of these reactions were found to be independent of the geometry of (24), both isomers of which were shown to be conflgurationally stable under the reaction conditions. Since the oxime stereochemistry defines the site of coordination to the boron atom, it seems likely that the (Z)-oxime isomer reacts preferentially through the chair-like transition state (28), while the ( )-oxime reactions proceed preferentially via boat-like transition state (27). Evidently, the chair-like arrangement... 

Sano. S. 3-Methyl-ot-himachalene is confirmed, and the 20. relative stereochemistry defined, by synthesis as the sex pheromone of the sandfly Lutzomyia longipalpis from Jacobina. Brazil. Chem. Commun. 1999, 4. 355-356. 21. 

The two structures in our example are identical and are rotated by only 1 20 h Clearly, rotation of a molecule docs not change its stereochemistry, Thus, the permutation descriptor of both representations should be (+ I). On this basis, we can define an equation where the number of transpositions is correlated with the permutation descriptors in an exponential term (Eq. (9)). 

Many chemical reactions proceed with a clearly defined stereochemistry, requiring the bonds to be broken and made in the reaction to have a specific geometrical arrangement. This is particularly true for reactions that are controlled by enzymes. 

Nonclassical ions, a term first used by John Roberts (an outstanding Caltech chemist and pioneer in the field), were defined by Paul Bartlett of Harvard as containing too few electrons to allow a pair for each bond i.e., they must contain delocalized (T-electrons. This is where the question stood in the early 1960s. The structure of the intermediate 2-norbornyl ion could only be suggested indirectly from rate (kinetic) data and observation of stereochemistry no direct observation or structural study was possible at the time. 

A mechanism in which the stereochemistry of the growing chain does exert an influence on the addition might exist, but at least two repeat units in the chain are required to define any such stereochemistry. Therefore this possibility is equivalent to the penultimate mechanism in copolymers. In this case the addition would be described in terms of conditional probabilities, just as Eq. (7.49) does for copolymers. Thus the probability of an isotactic triad controlled by the stereochemistry of the growing chain would be represented by the reaction... 

The need for simple names to describe complex structures has been met in several ways, the most straightforward of which is to use a trivial name giving little or no structural information e.g. morphine, opuntiol). Such names are.often based on the Latin name of the species from which the compound was isolated e.g. opuntiol from Opuntia eliator). While this is acceptable for a newly isolated compound of unknown structure, it is less satisfactory once the structure is established. What is needed is some means of establishing the relationship of the compound to others in the same class, without going into too much detail with regard to structure and stereochemistry. This can be achieved by defining, for a particular group of structures, a parent structure. 

Most parent structures consist essentially of an assembly of rings and/or chains, the degree of hydrogenation of which is defined (usually completely saturated or containing the maximum number of non-cumulative double bonds in cyclic portions), and having no attached functional substituents (the carbohydrates are a notable exception to this). The stereochemistry at all (or most) chiral centres is defined thus such parent structures are sometimes referred to as stereoparents . Some examples are shown (77)-(83). 

There are several general classes of pericyclic reactions for which orbital symmetry factors determine both the stereochemistry and relative reactivity. The first class that we will consider are electrocyclic reactions. An electrocyclic reaction is defined as the formation of a single bond between the ends of a linear conjugated system of n electrons and the reverse process. An example is the thermal ring opening of cyclobutenes to butadienes ... 

Lower oxidation states are rather sparsely represented for Zr and Hf. Even for Ti they are readily oxidized to +4 but they are undoubtedly well defined and, whatever arguments may be advanced against applying the description to Sc, there is no doubt that Ti is a transition metal . In aqueous solution Ti can be prepared by reduction of Ti, either with Zn and dilute acid or electrolytically, and it exists in dilute acids as the violet, octahedral [Ti(H20)6] + ion (p. 970). Although this is subject to a certain amount of hydrolysis, normal salts such as halides and sulfates can be separated. Zr and are known mainly as the trihalides or their derivatives and have no aqueous chemistry since they reduce water. Table 21.2 (p. 960) gives the oxidation states and stereochemistries found in the complexes of Ti, Zr and Hf along with illustrative examples. (See also pp. 1281-2.)... 

The coordination chemistry of the large, electropositive Ln ions is complicated, especially in solution, by ill-defined stereochemistries and uncertain coordination numbers. This is well illustrated by the aquo ions themselves.These are known for all the lanthanides, providing the solutions are moderately acidic to prevent hydrolysis, with hydration numbers probably about 8 or 9 but with reported values depending on the methods used to measure them. It is likely that the primary hydration number decreases as the cationic radius falls across the series. However, confusion arises because the polarization of the H2O molecules attached directly to the cation facilitates hydrogen bonding to other H2O molecules. As this tendency will be the greater, the smaller the cation, it is quite reasonable that the secondary hydration number increases across the series. 

The Diels-Alder reaction is one of the most useful synthetic reactions for the construction of the cyclohexane framework. Four contiguous stereogenic centers are created in a single operation, with the relative stereochemistry being defined by the usually ewdo-favoring transition state. 

In order to obtain good yields from a Weiss reaction sequence, the H+-concentration has to be adjusted properly in the reaction mixture. The reaction is usually carried out in a buffered, weakly acidic or weakly basic solution. By the Weiss reaction simple starting materials are converted into a complex product of defined stereochemistry. There is no simpler procedure for the synthesis of the l,5-c -disubstituted bicyclo[3.3.0]octane skeleton it has for example found application in the synthesis of polyquinanes. ... 

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